Polymerization of olefins

ABSTRACT

Various olefins may be polymerized using a catalyst systems containing selected α-diimine, urethane or urea ligands, some of them novel, complexed to nickel, palladium or other selected transition metals. The polymers are useful as molding resins and elastomers.

This application claims the benefit of U.S. Provisional Application No.60/094,502 filed Jul. 29, 1998, now pending.

FIELD OF THE INVENTION

Various nickel and palladium complexes, for example of α-diiminessubstituted at the carbon atoms by heteroatoms such as nitrogen oroxygen, and selected ureas and urethanes, may be used as polymerizationcatalysts for olefins such as ethylene. The palladium catalysts alsopolymerize polar comonomers.

TECHNICAL BACKGROUND

Recently polymerization catalysts containing late transition metals suchas palladium and nickel have been reported. Among these compounds arecomplexes of α-diimines (see World Patent Application 96/23010) andvarious other types of ligands (see U.S. Pat. No. 5,714,556). Thesecatalysts can, under various conditions, make unique polyolefins, suchas those that contain “abnormal” branching patterns when compared topolymers made by the well known Ziegler-Natta- and metallocene-typecatalysts. In addition some of these catalysts can polymerize olefinswhich are often not polymerizable with most catalysts based ontransition metal compounds, for example polar olefins such as olefinicesters. Therefore, new olefin polymerization catalysts containing latetransition metals are of great interest.

The use of palladium containing catalysts to polymerize olefins isdescribed in S. Mecking, et al., J. Am. Chem. Soc., vol. 120, p. 888-899(1998). Nickel diimine complexes as olefin polymerization catalysts aredescribed in L. K. Johnson, et al., J. Am. Chem. Soc., vol. 117, p.6414-6415 (1995), and L. K. Johnson, et al., J. Am. Chem. Soc., vol.118, p.267-268 (1996). None of the catalysts described herein aredescribed in these papers.

Certain iron, cobalt and molybdenum complexes of α-diimines havingnitrogen substituted in the backbone are described in M. Doring, et al.,Z. Anorg. Allg.

Chem., vol. 620, p. 551-560 (1994). None of these substituted α-diiminesor these metal complexes are claimed herein.

The reactions of various bis(imidoyl chlorides) of oxalic acid withamines, diamines and aminoalcohols to form various nitrogen and oxygensubstituted α-diimines is described in D. Lauder, et al., J. Prakt.Chem., vol. 337, p. 143-152 and ibid., p. 508-515 (1995). None of thesubstituted α-diimines enumerated in these papers is claimed herein:

SUMMARY OF THE INVENTION

This invention concerns a first process for the polymerization of one ormore olefins of the formula H₂C═CHR¹ and optionally one or more olefinsof the formula H₂C═CHR², comprising, contacting said olefins with acomplex containing a transition metal selected from the group consistingof palladium, nickel, titanium, zirconium, scandium, vanadium, chromium,iron, cobalt, and a rare earth metal and a ligand of the formula

which is an active polymerization catalyst, wherein:

each R¹ is independently hydrogen or alkyl;

each R² is independently substituted alkyl or —CO₂R⁵⁰;

A and E are each independently oxygen, sulfur, phosphorous or nitrogen;

R³ and R⁸ are each independently hydrocarbyl or substituted hydrocarbylprovided that the carbon atom bound to the nitrogen atom is bound to atleast two other carbon atoms;

R⁴, R⁵, R⁶ and R⁷ are each independently hydrocarbyl or substitutedhydrocarbyl;

Ar¹ and Ar² are each independently aryl or substituted aryl;

R⁹ and R¹⁰ are each independently hydrocarbyl or substitutedhydrocarbyl;

R⁵⁰ is hydrocarbyl or substituted hydrocarbyl;

and provided that:

when said ligand is (II) or (III) said transition metal is nickel;

when H₂C═CHR² is present a palladium complex is present;

the members of any one or more of the pairs R⁴ and R⁵, R⁶ and R⁷, R⁴ andR⁶, and R⁵ and R⁷ taken together may form a ring;

when A is oxygen or sulfur, R⁵ is not present; and

when E is oxygen or sulfur, R⁷ is not present.

This invention also concerns a second process for the polymerization ofone or more olefins of the formula H₂C═CHR¹ and optionally one or moreolefins of the formula H₂C═CHR², comprising, contacting said olefins, afirst compound of the formula

[Ar¹HNC(O)OR⁹]MX_(n),  (V)

or

[Ar¹HNC(O)NHR¹⁰]MX_(n),  (VI)

and:

(a) a second compound W, which is a neutral Lewis acid capable ofabstracting X⁻ from M to form WX⁻, and which is also capable oftransferring an alkyl group or a hydride to M, provided that WX⁻ is aweakly coordinating anion; or

(b) a combination of a third compound which is capable of transferringan alkyl or hydride group to M and a fourth compound which is a neutralLewis acid which is capable of abstracting X⁻, a hydride or an alkylgroup from M to form a weakly coordinating anion; or

(c) when at least one of X is a hydride or alkyl group, a fifth compoundwhich is a cationic Lewis or Bronsted acid whose counterion is a weaklycoordinating anion;

wherein:

M is Ni, Pd, Ti, Zr, Sc, V, Cr, Fe, Co or a rare earth metal;

each X is independently a monoanion;

n is equal to the oxidation number of M;

each R¹ is independently hydrogen or alkyl;

each R² is independently substituted alkyl or —CO₂R⁵⁰;

A and E are each independently oxygen, sulfur, phosphorous, or nitrogen;

R³ and R⁸ are each independently hydrocarbyl or substituted hydrocarbylprovided that the carbon atom bound to the nitrogen atom is bound to atleast two other carbon atoms;

R⁴, R⁵, R⁶ and R⁷ are each independently hydrocarbyl or substitutedhydrocarbyl;

Ar¹ and Ar² are each independently aryl or substituted aryl;

R⁹ and R¹⁰ are each independently hydrocarbyl or substitutedhydrocarbyl;

R⁵⁰ is hydrocarbyl or substituted hydrocarbyl;

and provided that

when said first compound is (II) or (III), M is Ni;

the members of any one or more of the pairs R⁴ and R⁵, R⁶ and R⁷, R⁴ andR⁶, and R⁵ and R⁷ taken together may form a ring;

when H₂C═CHR² is present a palladium complex is present;

when A is oxygen or sulfur, R⁵ is not present; and

when E is oxygen or sulfur, R⁷ is not present.

This invention also includes a compound of the formula

 [Ar¹HNC(O)OR⁹]MX_(n),  (V)

or

[Ar¹HNC(O)NHR¹⁰]MX_(n),  (VI)

wherein:

M is Ni, Pd, Ti, Zr, Sc, V, Cr, Fe, Co or a rare earth metal;

each X is independently a monoanion;

n is equal to the oxidation number of M;

A and E are each independently oxygen, sulfur, phosphorous, or nitrogen;

R³ and R⁸ are each independently hydrocarbyl or substituted hydrocarbylprovided that the carbon atom bound to the nitrogen atom is bound to atleast two other carbon atoms;

R⁴, R⁵, R⁶ and R⁷ are each independently hydrocarbyl or substitutedhydrocarbyl;

Ar¹ and Ar² are each independently aryl or substituted aryl;

R⁹ and R¹⁰ are each independently hydrocarbyl or substitutedhydrocarbyl;

and provided that

when said compound is (V) or (VI), M is Ni;

the members of any one or more of the pairs R⁴ and R⁵, R⁶ and R⁷, R⁴ andR⁶, and R⁵ and R⁷ taken together may form a ring;

when A is oxygen or sulfur, R⁵ is not present; and

when E is oxygen or sulfur, R⁷ is not present.

Also disclosed herein is a compound of the formula

wherein

A and E are each independently oxygen, sulfur, phosphorous, or nitrogen;

R⁴, R⁵, R⁶ and R⁷ are each independently hydrocarbyl or substitutedhydrocarbyl;

R¹¹ is hydrocarbyl or substituted hydrocarbyl containing 2 or morecarbon atoms, or a functional group;

R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;

and provided that

the members of any one or more of the pairs R⁴ and R⁵, R⁶ and R⁷, R⁴ andR⁶, and R⁵ and R⁷ taken together may form a ring;

any two of R¹¹, R¹², R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,

R¹⁹, and R²⁰ vicinal to one another taken together may form a ring withthe further proviso that if R¹¹ and R¹² are taken together to form aring, then R¹¹ and R¹² taken together contain at least 2 carbon atoms;

when A is oxygen or sulfur, R⁵ is not present; and

when E is oxygen or sulfur, R⁷ is not present.

DETAILS OF THE INVENTION

Herein, certain terms are used. Some of them are:

A “hydrocarbyl group” is a univalent group containing only carbon andhydrogen. If not otherwise stated, it is preferred that hydrocarbylgroups (and alkyl groups) herein contain 1 to about 30 carbon atoms.

By “substituted hydrocarbyl” herein is meant a hydrocarbyl group whichcontains one or more substituent groups which are inert under theprocess conditions to which the compound containing the groups issubjected. The substituent groups also do not substantially interferewith the process. If not otherwise stated, it is preferred thatsubstituted hydrocarbyl groups herein contain 1 to about 30 carbonatoms. Included in the meaning of “substituted” are heteroaromaticrings.

By “(inert) functional group” herein is meant a group other thanhydrocarbyl or substituted hydrocarbyl which is inert under the processconditions to which the compound containing the group is subjected. Thefunctional groups also do not substantially interfere with any processdescribed herein that the compound in which they are present may takepart. Examples of functional groups include halo (fluoro, chloro, bromoand iodo), trialkylsilyl, ether such as —OR²² wherein R²² is hydrocarbylor substituted hydrocarbyl. In cases in which the functional group maybe near a nickel or palladium atom the functional group should notcoordinate to the metal atom more strongly than the groups in thosecompounds are shown as coordinating to the metal atom, that is theyshould not displace the desired coordinating group.

By an “alkyl aluminum compound” is meant a compound in which at leastone alkyl group is bound to an aluminum atom. Other groups such asalkoxide, hydride, and halogen may also be bound to aluminum atoms inthe compound.

By “neutral Lewis base” is meant a compound, which is not an ion, whichcan act as a Lewis base. Examples of such compounds include ethers,amines, sulfides, and organic nitrites.

By “cationic Lewis acid” is meant a cation which can act as a Lewisacid. Examples of such cations are sodium and silver cations.

By relatively noncoordinating (or weakly coordinating) anions are meantthose anions as are generally referred to in the art in this manner, andthe coordinating ability of such anions is known and has been discussedin the literature, see for instance W. Beck., et al., Chem. Rev., vol.88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p.927-942 (1993), both of which are hereby included by reference. Amongsuch anions are those formed from the aluminum compounds mentionedpreviously and X⁻, including R³³ ₃AlX⁻, R³³ ₂AlClX⁻, R³³AlCl₂X⁻, and“R³³AlOX⁻”, wherein R³³ is alkyl. Other useful noncoordinating anionsinclude BAF⁻ {BAF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, SbF₆⁻, PF₆ ⁻, and BF₄ ⁻, trifluoromethanesulfonate, p-toluenesulfonate,(R_(f)SO₂)₂N⁻, and (C₆F₅)₄B⁻.

By an empty coordination site is meant a potential coordination sitethat does not have a ligand bound to it. Thus if an ethylene molecule isin the proximity of the empty coordination site, the ethylene moleculemay coordinate to the metal atom.

By a ligand that may add to an olefin is meant a ligand coordinated to ametal atom into which an olefin molecule as described above (or acoordinated olefin molecule) may insert to start or continue apolymerization. For instance, this may take the form of the reaction(wherein L is a ligand and the olefin is ethylene):

By a rare earth metal is meant one of lanthanum, cerium, praeseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

Compounds of formulas (I) and (VII) can be made by the reaction of thecorresponding bis(imidoyl chlorides) of oxalic acid with compoundscontaining primary or secondary amines, alcohols, phenols, thiols,phosphines, or a combination thereof, see for instance D. Lauder, etal., J. Prakt. Chem., vol. 337, p. 143-152 and ibid., p. 508-515 (1995),both of which are hereby included by reference, and the examples herein.

Compounds of formulas (II) and (III) may be made by the reaction of anorganic isocyanate with the corresponding organic hydroxy compound, orprimary or secondary amine, respectively.

The Ni and Pd and other metal complexes described herein may be made byvarious methods (depending on the other ligands present in the complex),and by methods described in World Patent Application 96/23010 and U.S.Pat. No. 5,714,556, both of which are hereby included by reference. TheExamples herein also illustrate such methods. These complexes may bepreformed, i.e., may be added to the polymerization process in a form inwhich the ligand (I), (II) or (III) is already complexed to thetransition metal, or may be formed in situ, i.e., the transition metal(compound) and ligand are added separately to the polymerizationprocess, but the desired complex forms in situ. This includes allinstances when precursors to the desired transition metal complex areadded. For instance the transition metal may be added in the form of anM[0] complex, such as bis(cyclooctadiene)nickel, in which the nickel maybe oxidized to Ni[II] by reaction with HY, wherein Y is a relativelynoncoordinating anion. Other methods of forming such complexes in situare found in World Patent Application 96/23010 and U.S. Pat. No.5,714,556.

In (I) and (VII), and in all other compounds in which these substituentsoccurs, it is preferred that:

A and E are each independently nitrogen or oxygen, more preferably bothA and E are nitrogen; and/or

A and E are both oxygen; and/or

A is nitrogen or phosphorous, more preferably nitrogen, and R⁴ and R⁵taken together for a ring; and/or

R⁴ and R⁶ taken together form a ring, more preferably —(CH₂)_(z)—wherein z is 2 or 3; and/or

R³ is

 wherein R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any of R²³, R²⁴, R²⁵, R²⁶ and R²⁷ vicinal to one another takentogether may form a ring; and/or

R⁸ is

 wherein R²⁸, R²⁹, R³⁰, R³¹ and R³² are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any of R²⁸, R²⁹, R³⁰, R³¹ and R³² vicinal to one another takentogether may form a ring. In another preferred compound (I) or (VII) Aand E taken together are part of a ring, where applicable in combinationwith any of the above.

In (II) or other compounds herein in which these groups occur, it ispreferred that:

Ar¹ is

 wherein R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any of R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ vicinal to one another takentogether may form a ring, and more preferably one or both of R³⁴ and R³⁸are alkyl containing 1 to 4 carbon atoms, and/or R³⁵, R³⁶ and R³⁷ arehydrogen; and/or

R⁹ is alkyl, substituted alkyl, aryl or substituted aryl, especiallyalkyl or

 wherein R³⁹, R⁴⁰, R⁴¹, R⁴² and R⁴³ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any of R³⁹, R⁴⁰, R⁴¹, R⁴² and R⁴³ vicinal to one another takentogether may form a ring, and more preferably one or both of R³⁹ and R⁴³are alkyl containing 1 to 4 carbon atoms, and/or R⁴⁰, R⁴¹ and R⁴² arehydrogen.

In (III) or other compounds herein in which these groups occur, it ispreferred that:

Ar² is

 wherein R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group, providedthat any of R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ vicinal to one another takentogether may form a ring, and more preferably one or both of R⁴⁴ and R⁴⁸are alkyl containing 1 to 4 carbon atoms, and/or R⁴⁵, R⁴⁶ and R⁴⁷ arehydrogen; and/or

R¹⁰ is alkyl or substituted alkyl, especially hydroxyl substitutedalkyl.

It is preferred that X is halide, alkyl, carboxylate or acetylacetonate,more preferably chloride, bromide or iodide. When X is alkyl it is morepreferred that M is Pd and only one of X is alkyl.

It is preferred that R¹ ig hydrogen or n-alkyl containing 1 to 18 carbonatoms, more preferably hydrogen or methyl, and especially preferablyhydrogen, or any combination thereof. It is also preferred that R² is—(CH₂)_(q)R⁴⁸ wherein q is 0 or an integer of 1 to 18 and R⁴⁸ is afunctional group, more preferably q is 0 and/or R⁴⁸ is CO₂R⁴⁹, whereinR⁴⁹ is hydrocarbyl or substituted hydrocarbyl, more preferablyhydrocarbyl, and especially preferably alkyl.

In all complexes one preferred metal is nickel. In other complexespreferred metals are Ti, Zr, Sc, V, Cr or a rare earth metal, especiallywith (I) when R⁴ and R⁵ taken together form a ring, and R⁶ and R⁷ takentogether do not form a ring.

In the first polymerization process described herein a nickel, palladiumor other metal complex is either added to the polymerization process orformed in situ in the process. In fact, more than one such complex maybe formed during the course of the process, for instance formation of aninitial complex and then reaction of that complex to form a living endedpolymer containing such a complex.

Examples of such complexes which may be formed initially in situ include

wherein R³ through R⁸ and M are as defined above, T¹ is hydride or alkylor any other anionic ligand into which ethylene can insert, Y is aneutral ligand capable of being displaced by ethylene or a vacantcoordination site, the “parallel lines” are an ethylene moleculecoordinated to the metal, and Q is a relatively non-coordinating anion.Complexes may be added directly to the process or formed in situ. Forinstance, (XIII) may be formed by the reaction of (IV) with a neutralLewis acid such as an alkyl aluminum compound. Another method of forminga complex in situ is adding a suitable nickel or palladium compound suchas nickel [II] acetylacetonate, (I) and an alkyl aluminum compound.Other metal salts in which anions similar to acetylacetonate arepresent, and which may be removed by reaction with the Lewis or Bronstedacid, may also be used. For instance metal halides and carboxylates(such as acetates) may be used, particularly if they are slightlysoluble in the process medium. It is preferred that these precursormetal salts be at least somewhat soluble in the process medium.

After the polymerization has started, the complex may be in a form suchas

wherein R³ through R⁸, M, and Q are as defined above, P is a divalentpolymeric group such as a (poly)ethylene group of the formula—(CH₂CH₂)_(x)— wherein x is an integer of 1 or more, and T² is an endgroup, for example the groups listed for T¹ above. Those skilled in theart will note that (xv) is in essence a polymer containing a so-calledliving end. It is preferred that M be in +2 oxidation state in thesecompounds. Compounds such as (XIII), (XIV) and (XV) may or may not bestable away from an environment similar to that of the is polymerizationprocess, but they may be detected by NMR spectroscopy, particularly oneor both of ¹H and ¹³C NMR, and particularly at lower temperatures. Suchtechniques, especially for polymerization “intermediates” of these typesare known, see for instance World Patent Application 96/23010,especially Examples 197-203.

(XIII), (XIV) and (XV) may also be used, in the absence of any“co-catalysts” or “activators” to polymerize one or more suitableolefins in a third polymerization process. Except for the ingredients inthe process, the process conditions for the third process, such astemperature pressure, polymerization medium, etc., may be the same asfor the first and second polymerization processes, and preferredconditions for those processes are also preferred for the thirdpolymerization process.

In the first, second and third polymerization processes herein, thetemperature at which the polymerization is carried out is about −100° C.to about +200° C., preferably about −60° C. to about 150° C., morepreferably about −20° C. to about 100° C. The pressure of the olefin (ifit is a gag) at which the polymerization is carried out is not critical,atmospheric pressure to about 275 MPa being a suitable range.

The polymerization processes herein may be run in the presence ofvarious liquids, particularly aprotic organic liquids. The catalystsystem, olefin, and polyolefin may be soluble or insoluble in theseliquids, but obviously these liquids should not prevent thepolymerization from occurring. Suitable liquids include alkanes,cycloalkanes, selected halogenated hydrocarbons, and aromatichydrocarbons. Specific useful solvents include hexane, toluene, benzene,methylene chloride, and 1,2,4-trichlorobenzene.

The olefin polymerizations herein may also initially be carried out inthe solid state by, for instance, supporting the nickel or palladiumcompound on a substrate such as silica or alumina, activating it withthe Lewis (such as W, for instance an alkylaluminum compound) orBronsted acid and exposing it to olefin. Alternatively, the support mayfirst be contacted (reacted) with W such as an alkylaluminum compound,and then contacted with an appropriate transition metal compound such as(IV), (V) or (VI). The support may also be able to take the place of theLewis or Bronsted acid, for instance an acidic clay such asmontmorillonite. Another method of making a supported catalyst is tostart a polymerization or at least make a transition metal complex ofanother olefin or oligomer of an olefin such as cyclopentene on asupport such as silica or alumina. These “heterogeneous” catalysts maybe used to catalyze polymerization in the gas phase or the liquid phase.By gas phase is meant that a gaseous olefin is transported to contactwith the catalyst particle.

In all of the polymerization processes described herein oligomers andpolymers of the various olefins are made. They may range in molecularweight from oligomeric olefins, to lower molecular weight oils andwaxes, to higher molecular weight polyolefins. One preferred product isa polymer with a degree of polymerization (DP) of about 10 or more,preferably about 40 or more. By “DP” is meant the average number ofrepeat (monomer) units in a polymer molecule.

Depending on their properties, the polymer made by the processesdescribed herein are useful in many ways. For instance if they arethermoplastics, they may be used as molding resins, for extrusion,films, etc. If they are elastomeric, they may be used as elastomers. Ifthey contain functionalized monomers such as acrylate esters, they areuseful for other purposes, see for instance World Patent Application96/23010.

Polyolefins are most often prepared by polymerization processes in whicha transition metal containing catalyst system is used. Depending on theprocess conditions used and the catalyst system chosen, polymers, eventhose made from the same monomer(s) may have varying properties. Some ofthe properties which may change are molecular weight and molecularweight distribution, crystallinity, melting point, and glass transitiontemperature. Except for molecular weight and molecular weightdistribution, branching can affect all the other properties mentioned.

It is known that certain transition metal containing polymerizationcatalysts including those disclosed herein, are especially useful invarying the branching in polyolefins made with them, see for instanceWorld Patent Applications 96/23010 and 97/02298, and U.S. patentapplication Ser. No. 09/006,628, filed Jan. 13, 1998, now U.S. Pat. No.6,060,569 and Ser. No. 09/006,536, filed Jan. 13, 1998 now U.S. Pat. No.6,174,975. It is also known that blends of distinct polymers, that varyfor instance in the properties listed above, may have advantageousproperties compared to “single” polymers. For instance it is known thatpolymers with broad or bimodal molecular weight distributions may bemelt processed (be shaped) more easily than narrower molecular weightdistribution polymers. Similarly, thermoplastics such as crystallinepolymers may often be toughened by blending with elastomeric polymers.

Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

In such a process the catalysts disclosed herein can be termed the firstactive polymerization catalyst. Monomers useful with these catalysts arethose described (and also preferred) above.

A second active polymerization catalyst (and optionally one or moreothers) is used in conjunction with the first active polymerizationcatalyst. The second active polymerization catalyst may be another latetransition metal catalyst, for example as described in World PatentApplications 96/23010 and 97/02298, and U.S. patent application Ser. No.09/006,628, filed Jan. 13, 1998, now U.S. Pat. No. 6,060,569 Ser. No.09/006,536, filed Jan. 13, 1998, [now U.S. Pat. No. 6,174,975] and Ser.No. 08/991,372, filed Dec. 16, 1997 [now U.S. Pat. No. 5,955,555]. Otheruseful types of catalysts may also be used for the second activepolymerization catalyst. For instance so-called Ziegler-Natta and/ormetallocene-type catalysts may also be used. These types of catalystsare well known in the polyolefin field, see for instance Angew. Chem.,Int. Ed. Engl., vol. 34, p. 1143-1170 (1995), European PatentApplication 416,815 and U.S. Pat. No. 5,198,401 for information aboutmetallocene-type catalysts, and J. Boor Jr., Ziegler-Natta Catalysts andPolymerizations, Academic Press, New York, 1979 for information aboutZiegler-Natta-type catalysts, all of which are hereby included byreference. Many of the useful polymerization conditions for all of thesetypes of catalysts and the first active polymerization catalystscoincide, so conditions for the polymerizations with first and secondactive polymerization catalysts are easily accessible. Oftentimes the“co-catalyst” or “activator” is needed for metallocene orZiegler-Natta-type polymerizations. In many instances the same compound,such as an alkylaluminum compound, may be used as an “activator” forsome or all of these various polymerization catalysts.

In one preferred process described herein the first olefin(s) [themonomer(s) polymerized by the first active polymerization catalyst] andsecond olefin(s) [the monomer(s) polymerized by the second activepolymerization catalyst] are identical, and preferred olefins in such aprocess are the same as described immediately above. The first and/orsecond olefins may also be a single olefin or a mixture of olefins tomake a copolymer. Again it is preferred that they be identicalparticularly in a process in which polymerization by the first andsecond active polymerization catalysts make polymer simultaneously.

In some processes herein the first active polymerization catalyst maypolymerize a monomer that may not be polymerized by said second activepolymerization catalyst, and/or vice versa. In that instance twochemically distinct polymers may be produced. In another scenario twomonomers would be present, with one polymerization catalyst producing acopolymer, and the other polymerization catalyst producing ahomopolymer, or two copolymers may be produced which vary in the molarproportion or repeat units from the various monomers. Other analogouscombinations will be evident to the artisan.

In another variation of this process one of the polymerization catalystsmakes an oligomer of an olefin, preferably ethylene, which oligomer hasthe formula R⁷⁰CH═CH₂, wherein R⁷⁰ is n-alkyl, preferably with an evennumber of carbon atoms. The other polymerization catalyst in the processthem (co)polymerizes this olefin, either by itself or preferably with atleast one other olefin, preferably ethylene, to form a branchedpolyolefin. Preparation of the oligomer (which is sometimes called anα-olefin) by a second active polymerization-type of catalyst can befound in World Patent Application 96/23010, and U.S. patent applicationSer. No. 09/005,965, filed Jan. 12, 1998 now U.S. Pat. No. 6,103,946.

Likewise, conditions for such polymerizations, using catalysts of thesecond active polymerization type, will also be found in the appropriateabove mentioned references.

Two chemically different active polymerization catalysts are used inthis polymerization process. The first active polymerization catalyst isdescribed in detail above. The second active polymerization catalyst mayalso meet the limitations of the first active polymerization catalyst,but must be chemically distinct. For instance, it may have a differenttransition metal present, and/or utilize a different type of ligandand/or the same type of ligand which differs in structure between thefirst and second active polymerization catalysts. In one preferredprocess, the ligand type and the metal are the same, but the ligandsdiffer in their substituents.

Included within the definition of two active polymerization catalystsare systems in which a single polymerization catalyst is added togetherwith another ligand, preferably the same type of ligand, which candisplace the original ligand coordinated to the metal of the originalactive polymerization catalyst, to produce in situ two differentpolymerization catalysts.

The molar ratio of the first active polymerization catalyst to thesecond active polymerization catalyst used will depend on the ratio ofpolymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

The polymers made by the first active polymerization catalyst and thesecond active polymerization catalyst may be made in sequence, i.e., apolymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence. Any of theprocesses applicable to the individual catalysts may be used in thispolymerization process with 2 or more catalysts, i.e., gas phase, liquidphase, continuous, etc.

The polymers produced by this process may vary in molecular weightand/or molecular weight distribution and/or melting point and/or levelof crystallinity, and/or glass transition temperature and/or otherfactors. For copolymers the polymers may differ in ratios of comonomersif the different polymerization catalysts polymerize the monomerspresent at different relative rates. The polymers produced are useful anmolding and extrusion resins and in films as for packaging. They mayhave advantages such as improved melt processing, toughness and improvedlow temperature properties.

Hydrogen may be used to lower the molecular weight of polyolefinproduced in the first or second processes. It is preferred that theamount of hydrogen present be about 0.01 to about 50 mole percent of theolefin present, preferably about 1 to about 20 mole percent. When liquidmonomers (olefins) are present, one may need to experiment briefly tofind the relative amounts of liquid monomers and hydrogen (as a gas). Ifboth the hydrogen and monomer(s) are gaseous, their relativeconcentrations may be regulated by their partial pressures.

In the Examples, certain abbreviations are used:

ΔH_(f)—heat of fusion

BAF—tetrakis[bis(3,5-trifluoromethyl)phenyl]borate

DMAP—4-dimethylaminopyridine

DSC—Differential scanning Calorimetry (at a heating rate of 15° C./min;first heat −150° C. to +160° C., second heat −150° C. to +250° C.)

EOC—end of chain

Et—ethyl

GPC—Gel Permeation Chromatography

MAO and PMAO—methylaluminoxane

Me—methyl

Mn—number average molecular weight

Mw—weight average molecular weight

PDI—polydispersity, Mw/Mn

RT—room temperature

TLC—Thin Layer Chromatography

Tg—glass transition temperature

Tm=melting point

TO—turnovers, moles of olefin polymerized per mole of transition metalcompound.

All pressures in the Examples are gauge pressures. Metal complexes aredesignated by the number of the ligand, the metal, and other ligands(neutral or charged) on the complex. For instance the complex of ligand4 with NiBr₂ is written as 4·NiBr₂.

In the Examples, certain compounds are made and/or used. Theirstructures are shown below.

EXAMPLES 1-13

Compounds 1-13 were synthesized according to equations 1-3 shown below.These syntheses are based upon literature methods: see (a) Lindauer, D.;Beckert, R.; Doring, M.; Fehling, P.; Gorls, H. J. Prakt. Chem. 1995,337, 143-152 and references therein and (b) Lindauer, D.; Beckert, R.;Billert, T.; Doring, M.; Gorls, H. J. Prakt. Chem. 1995, 337, 508-515and references therein. Compounds 8, 9b, 10, 11, 12 and 13 arehydrolysis products of the ArN═C(X)—C(X)═NAr product shown in equation3.

EXAMPLE 1 Synthesis of 1

In a drybox, a 50 mL round-bottom flask was charged withPhN═C(Cl)—C(Cl)═NPh (0.693 g, 2.5 mmol), pentafluorophenol (0.965 g, 5mmol), DMAP (0.915 g, 5 mmol) and anhydrous toluene (15 mL) andstoppered. The flask was moved to the hood and refluxed under N₂ forabout 3 h, while the reaction was monitored by TLC (5% ethylacetate/hexane). The precipitate (DMAP.HCl) was removed by filtrationand rinsed well with toluene. Solvent removal yield an oily solid, whichwas purified by column chromatography (silica gel, 5% ethylacetate/hexane). A white solid (0.822 g, 57%) was obtained: ¹H NMR(CDCl₃) δ 7.15 (m, 6, H_(Ph)), 6.52 (m, 4, H_(Ph)); ¹³C NMR (CDCl₃) δ146.5 and 143.25 (N═C—C═N and Ph: C_(ipso)), 142.1 (d of d, J=248, C₆F₅:C_(o)), 140.5 (d of t, J=258, C₆F₅: C_(p)), 138.8 (d of t, J=253, C₆F₅:C_(m)), 128.8, 125.7 and 120.6 (Ph: C_(o), C_(m), and C_(p)); ¹⁹F NMR(CDCl₃) δ −151.6 (d, F_(o)), −158.02 (t, F_(p)), −162.6 (t, F_(m)). [Nopeak was apparent in the ¹H NMR spectrum that would be indicative of theNH proton of the potential hydrolysis product PhNHC(O)(OC₆F₅).]

EXAMPLE 2 Synthesis of 2

In a hood, a 100 mL round-bottom flask was charged withPhN═C(Cl)—C(Cl)═NPh (1.111 g, 4 mmol), tetrabutylammonium chloride(0.078 g, 0.2 mmol), phenol (0.760 g, 8 mmol) and methylene chloride (20mL). Sodium hydroxide (400 μL, 25 M) and water (500 μL) were added viasyringe. The reaction was refluxed gently until starting material haddisappeared by TLC (5% ethyl acetate/hexane). The aqueous layer wasextracted with methylene chloride (3×10 mL) and the organic layers werecombined and dried over MgSO₄. The solvent was removed in vacuo and theproduct was recrystallized from hot hexane. After drying the productunder vacuum, 1.006 g (64%) of white powder was obtained: ¹H NMR (CDCl₃)δ 7.29 (t, 2, H_(m)), 7.17 (t, 2, H′_(m)), 7.12 (t, 1, H_(p)), 7.03 (t,1, H′_(p)), 6.95 (d, 2, H_(o)), 6.69 (d, 2, H′_(o)); ¹³C NMR (CDCl₃) δ151.9, 151.3, and 145.0 (C_(ipso), C′_(ipso), N═C—C═N), 129.4, 128.5,125.8, 124.5, 121.8, and 121.1 (Ph: C_(o), C_(m), C_(p); Ph′: C_(o),C_(m), C_(p)). [No peak was apparent in the ¹H NMR spectrum that wouldhe indicative of the NH proton of the potential hydrolysis productPhNHC(O)(OPh).]

EXAMPLE 3 Synthesis of 3

In a drybox, a small vial was charged with 0.277 g (1 mmol) ofPhN═C(Cl)—C(Cl)═NPh, the sodium salt of 2,5-dimethylpyrrole (0.239 g, 2mmol) and anhydrous tetrahydrofuran (10 mL) and capped. The vial wastransferred to the hood and the reaction was allowed to stir at RT andmonitored by TLC (5% ethyl acetate/hexane) until no starting materialwas present (about 24 h). The reaction was filtered to remove the NaClprecipitate, which was then rinsed with THF. The solvent was removedunder vacuum and the product was purified by column chromatography(silica gel, 5% ethyl acetate/hexane). A solid (0.145 g, 37%) wasobtained: ¹H NMR (THF-d₈) δ 7.3-7.0 (m, 6, Ph: H_(m) and H_(p)), 6.62(d, 4, Ph: H_(o)), 5.75 (s, 4, H_(pyrrole)), 2.05 (s, 12, Me); ¹³C/APTNMR (CDCl₃) δ 147.9 and 145.3 (Ph: C_(ipso) and N═C—C═N), 127.2(pyrrole: C—Me), 128.4, 127.6, and 123.6 (Ph: C₀, C_(m), and C_(p));107.6 (pyrrole: CH), 13.1 (Me). [No peak was apparent in the ¹H NMRspectrum that would be indicative of the NH proton of the potentialhydrolysis product PhNHC(O)(2,5-dimethylpyrrole).

EXAMPLE 4 Synthesis of 4

In a drybox, a small vial was charged with 2.080 g (7.5 mmol) ofPhN═C(Cl)—C(Cl)═NPh and anhydrous toluene (10 mL). Triethylamine (2.10μL, 15 mmol) was added via syringe and capped. The vial was transferredto the hood and N,N′-dimethylethylenediamine (800 μL, 7.5 mmol) wasadded via syringe. The reaction became very warm and a precipitateformed quickly. The reaction mixture was allowed to stir for about 24 hand then filtered to remove NEt₃.HCl, which was rinsed well withtoluene. The solvent was removed under vacuum to give an oil. Diethylether was added to precipitate a solid, which was collected on a frit. Apale yellow orange powder (1.336 g, 47%) was isolated: ¹H NMR (CDCl₃) δ6.85 (t, 4, H_(m)), 6.74 (t, 2, H_(p)), 6.10 (t, 4, H_(o)), 3.82 and3.02 (br s of 2H and overlapping br and sharp singlets of 8H, CH₂ andMe); ¹³C NMR (CDCl₃) δ 148.6 and 148.2 (Ph: C_(ipso) and N═C—C═N),128.0, 121.7 and 121.3 (Ph: C_(o), C_(m), and C_(p)), 49.8 (CH₂), 36.4(NCH₃); MW calcd for C₁₈H₂₀N₄ 292.39 g/mol; MS (CIMS) 293.0 m/z (M+1).

EXAMPLE 5 Synthesis of 5

In a drybox, a 50 mL round-bottom flask was charged with 1.666 g (5mmol) of ArN═C(Cl)—C(Cl)═NAr (Ar=2,6—C₆H₃—Me₂) and anhydrous toluene (10mL). Triethylamine (1.4 mL, 10 mmol) was added via syringe and capped.The flask was transferred to the hood where N,N′-dimethylethylenediamine(540 μL, 5 mmol) was added via syringe. The reaction was allowed to stirat RT for about 48 h; at this point, TLC (5% ethyl acetate/hexane)indicated that starting material was still present. Therefore, thereaction was heated gently for about 24 h and checked again by TLC. Theprecipitate (NEt₃.HCl) was removed via filtration and rinsed well withtoluene. The solvent was removed under vacuum. Diethyl ether was addedto precipitate the product, which was collected. The filtrate wasreduced in volume and hexane added to precipitate more of the product.All fractions were combined and rinsed with hexane, collected and driedunder vacuum. The product (0.782 g, 45%) was isolated as a pale yellowpowder. ¹H and ¹³C NMR regonances are broad at RT and are thereforereported at 60° C., where they are sharper: ¹H NMR (CDCl₃, 60° C.) δ6.84 (d, 4, H_(m)), 6.68 (t, 2, H_(p)), 3.41 (s, 4, CH₂), 2.78 (s, 6,NMe), 1.86 (s, 12, Ar: Me); ¹³C/APT NMR (CDCl₃, 60° C.) δ 148.4 and145.5 (Ar: C_(ipso) and N═C—C═N), 127.2 (Ar: C_(m)), 126.9 (Ar: C_(o)),120.7 (Ar: C_(p)), 49.3 (CH₂), 37.2 (NMe), 18.2 (Ar: Me); MW calcd forC₂₂H₂₈N₄ 348.5 g/mol; MS (CIMS) 349.1 m/z (M+1).

EXAMPLE 6 Synthesis of 6

In a drybox, a small vial was charged with 2.232 g (5 mmol) ofArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃-(i-Pr)₂), DMAP (1.222 g, 10 mmol) andanhydrous toluene (10 mL) and capped. The vial was transferred to thehood and N,N′-dimethylethylenediamine (532 μL, 5 mmol) was added viasyringe. The reaction mixture became clear and then after approximately5 min a precipitate formed. The reaction mixture was allowed to stir atRT for approximately 2 days and followed by TLC (5% ethylacetate/hexane). CH₂Cl₂ was added to the reaction mixture to dissolvethe precipitate and the resulting solution was extracted with 5%HCl_((aq))(3×25 mL), and the organic layer was dried over MgSO₄. Thesolvent was removed under vacuum and the resulting solid wasrecrystallized from hot hexane to give 0.843 g (37%) of a pale yellowpowder: ¹H NMR (CDCl₃) δ 7.5-7.0 (m, 6, H_(aryl)), 3.56 (s, 4, CH₂),3.14 (s, 6, NMe), 3.08 (septet, 4, CHMe₂), 1.17 (d, 24, CHMe₂)

EXAMPLE 7 Synthesis of 7

In a drybox, a 50 mL round-bottom flask was charged with 1.666 g (5mmol) of ArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃—Me₂) and anhydrous toluene (10mL). Triethylamine (1.4 mL, 10 mmol) was added via syringe and the flaskwas capped and transferred to the hood. In the hood,N,N′-dimethyl-1,3-propanediamine (620 μL, 5 mmol) was added via syringe.The reaction mixture was allowed to stir at RT for about 48 h; at thispoint, TLC (5% ethyl acetate/hexane) showed that starting material wasstill present. Therefore, the reaction was heated gently for about 24 hand checked again by TLC. The precipitate (NEt₃.HCl) was removed viafiltration and rinsed well with toluene. The solvent was removed undervacuum. Diethyl ether was added to precipitate the product, which wascollected. The filtrate was reduced in volume and hexane added tofurther precipitate the product. All fractions were combined and rinsedwith hexane, collected and dried under vacuum to give 0.844 g (47%) ofan off-white powder: ¹H NMR (CDCl₃, 500 MHz, RT) δ 6.71 (br s, 4,H_(m)), 6.61 (t, 2, H_(p)), 1.79 (pentet, 2, CH₂CH₂CH₂); the followingresonances correspond to the NMe, Ar: Me, and —CH₂CH₂CH₂— resonances:3.63 (br s), 3.07 (br s), 2.75 (br s), 2.01 (br s), 1.30 (br s); ¹³CNMR/APT (CD₂Cl₂) δ 151, 146.7, and 130.4 (Ar: C_(ipso), C_(o) andN═C—C═N), 127.1 (Ar: C_(m)), 121.3 (Ar: C_(p)), 47.9 (NCH₂CH₂CH₂N), 36.0(NMe), 24.5 (NCH₂CH₂CH₂N), 17.6 (Ar: Me); MW calcd for C₂₃H₃₀N₄ 362.5g/mol; MS (CIMS) 363.0 m/z (M+1).

EXAMPLE 8 Synthesis of 8

In a drybox, a small vial was charged with 2.232 g (5 mmol) ofArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃-(i-Pr)₂), DMAP (1.229 g, 10 mmol) andanhydrous toluene (10 mL) and capped. In the hood,2-(methylamino)ethanol (420 μL, 5 mmol) was added via syringe. Thereaction mixture was allowed to stir at RT for about 48 h and monitoredby TLC (5% ethyl acetate/hexane). Next, the reaction mixture was dilutedin CH₂Cl₂ and the resulting solution was extracted with 5% HCl (aq)(3×25 mL), and the organic layer was dried over MgSO₄. After solventremoval, the product was washed with hexane and then dried in vacuo togive 0.986 g of a pale yellow solid: ¹H NMR (CDCl₃) δ 7.40-6.56 (m, 3,H_(aryl)), 6.31 (s, 1, NH or OH), 3.65 (t, 2, CH₂), 3.41 (t, 2, CH₂),2.99 (septet, 2, CHMe₂), 2.92 (s, 3, Me), 1.08 (m, 12, CHMe₂). [Theproduct contains some impurities that make some NMR assignments,particularly integrations, uncertain. The structure of the compound isproposed to be the hydrolysis product shown above on the basis of theappearance of the 6.31 ppm —NH or —OH resonance.]

EXAMPLE 9 Synthesis of 9a and 9b

In a drybox, a small vial was charged with 0.831 g (3 mmol) ofPhN═C(Cl)—C(Cl)═NPh, sodium 2,6-diisopropylphenoxide (1.201 g, 6 mmol)and anhydrous tetrahydrofuran (10 mL) and capped. The vial wastransferred to the hood, and the reaction mixture was allowed to stir atRT for approximately 2 days, until TLC (5% ethyl acetate/hexane) showedno starting material. Sodium chloride was removed by filtration andrinsed well with THF. The solvent was removed under vacuum and theremaining solid was recrystallized from hot hexane. The product wasisolated and dried in vacuo to yield 1.326 g (79%) of a yellow-orangesolid as a mixture of 9a and 9b in a 6.7 to 1 ratio. 9a: ¹H NMR (CDCl₃)δ 7.2-6.5 (m, 16, H_(aryl)), 2.99 (septet, 4, CHMe₂), 1.13 (d, 12,CHMeMe′), 1.06 (d, 12, CHMeMe′); ¹³C/APT NMR (CDCl₃) δ 151.0, 146.7,145.2, and 140.9 (Ph: C_(ipso); Ar: C_(ipso), C_(o); N═C—C═N), 128.2,125.6, 124.1 and 120.6 (Ph: C_(o), C_(m), C_(p); Ar: C_(m), C_(p)), 26.9(CHMe₂), 24.1 and 23.3 (CHMeMe′); MW calcd for C₃₈H₄₄N₂O₂ 560.79 g/mol;MS (CIMS) 561.4 m/z (M+1). 9b: ¹H NMR (CDCl₃, non-aromatic resonancesonly) δ 4.69 (NH), 3.08 (septet, 2, CHMe₂), 1.20 (d, 12, CHMe₂); MWcalcd for C₁₉H₂₃O₂N 297.4 g/mol; MS (CIMS) 297.9 m/z (M+1).

EXAMPLE 10 Synthesis of 10

In a drybox, a small vial was charged with 3.341 g (7.5 mmol) ofArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃-(i-Pr)₂), anhydrous sodium methoxide(0.854 g, 15.75 mmol), and anhydrous methanol (10 mL) and capped. Thevial was transferred to the hood, and the reaction mixture was allowedto stir at RT for about 3 days until TLC showed little starting materialpresent. The white solid was filtered off and rinsed with methanol.Next, the solvent was removed and the product was dried under vacuum.The solid was then washed with hexane and dried in vacuo. A whitecrystalline solid (1.446 g, 44%) was obtained. Restricted rotation aboutthe amide bond results in the observation of two rotamers at RT inapproximately a 1.16 to 1 ratio. Only one set of resonances is observedat 60° C.: ¹H NMR (CDCl₃, RT, 500 MHz) δ 7.33 (t, 1, Ar: H_(p)), 7.21(d, 2, Ar: H_(m)), 6.49 and 6.10 (s, NH and NH′), 3.82 and 3.69 (OMe andOMe′), 3.22 (br s, 2, CHMe₂), 1.25 (d, 12, CHMe₂); ¹H NMR (CDCl₃, 60°C., 500 MHz) δ 7.32 (t, 1, Ar; H_(p)), 7.20 (d, 2, Ar: H_(m)), 6.08 (brs, 1, NH), 3.76 (br s, 3, OMe), 3.23 (septet, 2, CHMe₂), 1.26 (d, 12,CHMe₂); ¹³C NMR (CDCl₃, RT, 125 MHz) δ 156.3, 146.9 and 131.1 (Ar:C_(ipso), C_(o); C═O), 127.9 and 123.5 (Ar: C_(m), C_(p)), 52.4 (OCH₃),28.6 (CHMe₂), 23.5 (CHMe₂); MW calcd for C₁₄H₂₁O₂N 235.33 g/mol; MS(CIMS) 236.0 m/z (M+1).

EXAMPLE 11 Synthesis of 11

In the drybox, a small vial was charged with 2.229 g (5 mmol) ofArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃-(i-Pr)₂), triethylamine (1.4 mL, 10mmol), 1-aminopropanol (400 μL, 5 mmol), and anhydrous toluene (10 mL)and capped. The reaction mixture was allowed to stir at RT for about 7days. During this time, a precipitate (NEt₃.HCl) formed, which wasremoved via filtration and rinsed well with toluene. The solvent wasremoved under vacuum, and the product was washed with hexane and pumpeddry to give 0.444 g (20%) of a pale yellow powder: ¹H NMR (CDCl₃) δ 7.26(t, 1, H_(p)), 7.14 (d, 2, H_(m)), 6.15 and 4.52 (s, 1 each, NH , NH′ orOH), 3.75 (m, 1, CHMeO), 3.23 (m, 3, CHH′NH and CHMe₂), 3.00 (m, 2,CHH′NH), 1.14 (mt 12, CHMe₂), 1.03 (d, 3, CHMeO); ¹³C/APT NMR (CDCl₃)159.1, 147.9 and 130.8 (C═O, Ar: C_(ipso), C_(o)), 129.0 (Ar: C_(p)),124.1 (Ar: C_(m)), 68.2 (OCHMe), 47.9 (CH₂), 28.3 (CHMe₂), 24.3 and 23.1(CHMeMe′), 20.6 (OCHMe); MW calcd for C₁₆H₂₆O₂N₂ 278.40 g/mol; MS (CIMS)2790 m/z (M+1).

EXAMPLE 12 Synthesis of 12

In a drybox, a small vial was charged with 2.234 g (5 mmol) ofArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃-(i-Pr)₂), triethylamine (1.4 mL, 10mmol), dl-alaninol (400 μL, 5 mmol), and anhydrous toluene (10 mL) andcapped. The reaction mixture was allowed to stir at RT for about 48 hduring which time a thick precipitate formed. Next, the precipitate(NEt₃.HCl) was removed via filtration and rinsed well with toluene. Thesolvent was removed under vacuum and the product was washed with hexaneand dried in vacuo to give 0.592 g (26%) of a pale yellow powder: ¹H NMR(CDCl₃) δ 7.27 (t, 1, H_(p)), 7.15 (d, 2, H_(m)), 6.03 and 4.18 (s, 1each, NH, NH′ or OH), 3.86 (m, 1, CHMeN), 3.50 (m, 1, CHH′O), 3.36 (m,1, CHH′O), 3.20 (m, 2, CRMe₂), 1.12 (m, 12, CHMe₂), 0.98 (d, 3, CHMeNH);¹³C/APT NMR (CDCl₃) δ 157.1, 147.7, 130.7 (C═O, Ar: C_(ipso), C_(o)),128.8 (Ar: C_(p)), 123.2 (Ar: C_(m)), 67.6 (CH₂), 48.3 (CHMeN), 28.1(CHMe₂), 24.6 and 24.3 (CHMeMe′), 17.2 (CHMeN); MW calcd for C₁₆H₂₆O₂N₂278.40 g/mol; MS (CIMS) 279.0 m/z (M+1).

EXAMPLE 13 Synthesis of 13

In a drybox, a small vial was charred with 2.229 g (5 mmol) ofArN═C(Cl)—C(Cl)═NAr (Ar=2,6-C₆H₃-(i-Pr)₂), triethylamine (1.40 mL, 10mmol), 3-amino-1-propanol (400 μL, 5 mmol), and anhydrous toluene (10mL) and capped. The reaction mixture was allowed to stir at RT for about3-4 days during which time a thick precipitate formed. The reactionmixture was diluted with CH₂Cl₂ and the resulting solution was extractedwith 5% HCl(aq) (2×25 mL) and dried over MgSO₄. The solvent was removedand the product was washed with hexane and dried in vacuo to yield 0.592g (26%) of a white powder: ¹H NMR (CDCl₃) 7.37 (t, 1, H_(p)), 7.24 (d,2, H_(m)), 6.40 4.45 and 4.04 (br s, 1 each, NH, NH′ and OH), 3.64 (t,2, CH₂), 3.37 (t, 2, CH₂), 3.30 (septet, 2, CHMe₂), 1.59 (pentet, 2,CH₂), 1.22 (br m, 12, CHMe₂); ¹³C/APT NMR (CDCl₃) δ 158.8, 145.6 and128.8 (C═O; Ar: C_(ipso), C_(o)), 125.7 (Ar: C_(p)), 123.3 (Ar: C_(m)),58.2, 33.7 and 32.9 (CH₂CH₂CH₂), 28.2 (CHMe₂), 24.1 and 22.8 (CHMeMe′);MW calcd for C₁₆H₂₆O₂N₂ 278.40 g/mol; MS (CIMS) 2790 m/z (M+1).

EXAMPLE 14 Synthesis of 5·PdMeCl

In the drybox, compound 5 (255 mg, 0.731 mmol) and CODPdMeCl (194 mg,0.731 mmol) were dissolved in ˜15 mL of CH₂Cl₂. After being stirredovernight, the reaction mixture was filtered and the solvent was removedin vacuo. The resulting yellow powder was washed with Et₂O and dried(272 mg, 73.5%): ¹H NMR (CD₂Cl₂) δ 7.4-7.0 (m, 6, H_(aryl)), 3.57 (s, 4,NCH₂CH₂N′), 2.68 and 2.67 (s, 3 each, NMe, N′M), 2.62 and 2.59 (s, 6each, Ar, Ar′: Me), 0.00 (s, 3, PdMe).

EXAMPLE 15 Synthesis of 7·PdMeCl

In the drybox, compound 7 (113 mg, 0.312 mmol) and CODPdMeCl (82.6 mg,0.312 mmol) were suspended in ˜15 mL of Et₂O. After being stirredovernight, the reaction mixture was allowed to settle and the solventwas decanted. The resulting yellow powder was washed twice more withEt₂O and then dried in vacuo (92.6 mg, 57.1%): ¹H NMR (CD₂Cl₂) δ 7.2-7.0(m, 6, H_(aryl)), 3.35 (t, 4, NCH₂CH₂CH₂N), 2.51 and 2.46 (s, 6 each,Ar, Ar′: Me), 2.40 and 2.38 (s, 3 each, NMe, N′Me), 2.08 (pentet, 2,NCH₂CH₂CH₂N′), 0.00 (s, 3, PdMe).

EXAMPLE 16 Synthesis of [5·Pd(Me)(NCMe)]BAF

In the drybox at RT, 1 mL of CH₃CN and 14 mL of Et₂O were added to amixture of 5.PdMeCl (272 mg, 0.538 mmol) and NABAF (476 mg, 0.538 mmol).The reaction mixture was stirred overnight, sodium chloride was removedvia filtration, and the solvent was removed in vacuo to give 595 mg(80.5%) of a pale orange powder: ¹NMR (CD₂Cl₂) δ 7.82 (s, 8, BAF:H_(o)), 7.67 (s, 4, BAF: H_(p)), 7.3-6.9 (m, 6, H_(aryl)), 3.49 (s, 4,NCH₂CH₂N′), 2.65 and 2.56 (s, 3 each, NMe, N′Me), 2.45 and 2.37 (s, 6each, Ar, Ar′: Me), 1.76 (NCMe), 0.00 (PdMe).

EXAMPLE 17 Synthesis of [7·Pd(Me)(NCMe)]BAF

In the drybox at RT, 1 mL of CH₃CN and 14 mL of Et₂O were added to amixture of 7.PdMeCl (92.6 mg, 0.178 mmol) and NaBAF (158 mg, 0.178mmol). The reaction mixture was stirred overnight, sodium chloride wasremoved via filtration, and the solvent was removed in vacuo to give 201mg (81.4%) of a yellow powder: ¹H NMR (CD₂Cl₂) δ 7.69 (s, 8, BAF:H_(o)), 7.51 (s, 4, BAF: H_(p)), 7.2-6.9 (m, 6, H_(aryl)), 3.29 and 3.27(t, 2 each, NCH₂CH₂CH₂N′), 2.37 and 2.29 (s, 3 each, NMe, N′Me), 2.35and 2.28 (s, 6 each, Ar, Ar′: Me), 1.98 (pentet, 2, NCH₂CH₂CH₂N′), 1.64(s, 3, NCMe), 0.01 (s, 3, PdMe).

EXAMPLE 18 Ethylene Polymerization by [5·Pd(Me)(NCMe)]BAF

A 40 mL CH₂Cl₂ solution of [5.Pd(Me)(NCMe)]BAF (137 mg, 0.1 mmol) wasstirred and placed under 0 kPa (1 atm) of ethylene for 72 h. Followingprecipitation of the reaction mixture into methanol, filtration, andvacuum drying, polyethylene (6.35 g; 2,264 TO) was isolated: 143 totalMe/1000 CH₂; M_(w)=50,087; M_(n)=28,027; PDI=1.54.

EXAMPLES 19 AND 20 Ethylene/Methyl Acrylate Copolymerization by[5·Pd(Me)(NCMe)]BAF or [7.Pd (Me)(NCME)]BAF

Copolymerizations of ethylene and methyl acrylate catalyzed by[(ArN═C(X)—C(X)═NAr)Pd(Me)(NCMe)]BAF (0.1 mmol) were carried out at RTunder 0 kPa (1 atm) of ethylene in a 40 mL CH₂Cl₂ solution which was 1.2M in methyl acrylate. Copolymerization results for the palladiumcatalyst derived from ligands 5 and 7 are reported in Table 1.

TABLE 1 Ethylene (E)/methyl acrylate (MA) copolymerizations catalyzed by[(ArN═C(X)—C(X)═NAr)Pd(Me)(NCMe)]BAF. TON MA Incorp. Total Me Ex LigandE/MA (mol %) M_(n)/PDI per 1000 CH₂ 19

97/27 22% 7700/1.5 157 20

36/13 26% 6700/1.8 233

EXAMPLES 21-26 General Procedure for the Synthesis of (Ligand)NiBr₂Complexes

Under an inert atmosphere, a small vial was charged with1,2-dimethoxyethane nickel dibromide (0.20 mmol to 0.30 mmol), ligand (1equiv) and anhydrous CH₂Cl₂ (10 mL) and capped. The reaction mixture wasallowed to stir for about 48 h and then filtered through a frit withCelite, rinsing w ell with anhydrous CH₂Cl₂. After removal of solventunder vacuum, the product was washed with anhydrous hexane, collected ona frit, transferred to a vial, and dried under vacuum.

EXAMPLE 21 Synthesis of 5·NiBr₂

The above general procedure was followed on a 0.20 mmol scale; yield: 56mg (49%) pale brown powder. This compound was recrystallized frommethylene chloride and a x-ray crystal structure obtained using anEnraf-Nonius CAD4 diffractometer and MoKalpha radiation. The compoundhad the following characteristics: monoclinic, C2/c (No. 15),a=11.648(2)Å, b=14.302(2)Å, c=13.995(4)Å, beta=104.71(2)°, T=−75° C.,Vol=2255.0 Å³, Z=4, Formula weight 565.01, Density 1.664 g/cc,μ(Mo)=43.90 cm⁻¹. The crystal structure indicated that this ligand was abidentate ligand to the nickel atom coordinated with the imino nitrogenatoms.

EXAMPLE 22 Synthesis of 6·NiBr₂

The above general procedure was followed on a 0.20 mmol scale; yield: 76mg (56%) mint green powder.

EXAMPLE 23 Synthesis of 8·NiBr₂

The above general procedure was followed on a 0.25 mmol scale; yield:120 mg (72%) yellow solid.

EXAMPLE 24 Synthesis of 11·NiBr₂

The above general procedure was followed on a 0.25 mmol scale; yield:173 mg mint green solid.

EXAMPLE 25 Synthesis of 12·NiBr₂

The above general procedure was followed on a 0.25 mmol scale; yield:179 mg mint green solid.

EXAMPLE 26 Synthesis of 13·NiBr₂

The above general procedure was followed on a 0.20 mmol scale; yield:126 mg pale green solid.

EXAMPLE 27-32 Ethylene Polymerizations with Ligand·NiBr₂ Complexes

In a drybox, a thick-walled Schlenk flask was charged with theligand·NiBr₂ complex, 20 mL of toluene and a stir bar. The vessel wassealed and transferred to a Schlenk line in the hood and purged firstwith nitrogen and then with ethylene. Polymethylaluminoxane/toluene(PMAO)(9.5% Al, 1.4 mmol Al) was then quickly added and the reactionmixture was stirred under 28-35 kPa of ethylene for 19.5 h. The reactionmixture was quenched with 15 mL of 90/10 methanol/HCl. The polymer wascollected on a frit, rinsed with methanol and acetone and then driedovernight. The polymer was submitted for the following analyses: ¹H NMR,GPC and DSC.

TABLE 2 Ethylene polymerization screening with MAO activation of ligandNiBr₂. Ex Ligand Yield PE DSC/¹H NMR GPC 27  5 0.523 g T_(m) = 86.3° C.M_(w) = 806,122 311 TO ΔH_(f) = 21.71 J/g M_(n) = 192,786 NMR: insoluble28  6 2.630 g T_(g) = −65.45° C. M_(w) = 73,519 1560 TO NMR: 181.1Me/1000 CH₂ M_(n) = 39,317 29  8 0.819 g T_(g) = −94.05° C. M_(w) =637,232 487 TO T_(m) = 104.84° C. M_(n) = 222,280 ΔH_(f) = 46.65 J/g 3011 0.678 g T_(g) = −75, −30° C. M_(w) = 931,625 403 TO T_(m) = 105, 120°C. M_(n) = 491,427 ΔH_(f) = 4.6, 0.94 J/g 31 12 0.551 g T_(g) = 101.05°C. M_(w) = 627,620 327 TO T_(m) = 102.58° C. M_(n) = 111,466 ΔHf = 90.56J/g 32 13 0.431 g T_(m) = 104.80° C. M_(w) = 878,578 260 TO ΔH_(f) =18.79 J/g M_(n) = 243,875 NMR: insoluble

EXAMPLE 33

A mixture of 0.075 g (0.21 mmol) 7 and 0.060 g (0.19 mmol) nickeldibromide-dimethoxyethane complex in 3 mL methylene chloride was stirredat RT under nitrogen for 20 h and then was rotovapped to dryness,yielding 0.115 g (98%) of the NiBr₂ complex of 7 as a tan powder.

A 600-mL Parr® autoclave (connected to a 1 L ethylene reservoir tank)was loaded with 200 mL dry hexane (dried over silica-supported MAO). Thesolvent was stirred and saturated with ethylene at 60° C. and 200 kpag.The autoclave was vented and a red solution of 2.0 mg (0.0034 mmol) ofthe above complex and 1 mL modified methylaluminoxane (Akzo MMAO-3A;nominal 1.7M in heptane; contains about 30% isobutyl groups) in 3 mLtoluene (complex and MMAO were mixed about 1 min before injection) wastaken up into a 5-mL syringe and was quickly injected into the autoclavethrough a head port. The autoclave was immediately pressured to 1.03MPag with ethylene and was stirred in a 60° C. water bath for 1 h asethylene was fed and the 1-L ethylene reservoir tank pressure drop wasmonitored with time (see data below). The ethylene was then vented andthe clear solution was diluted with acetone to precipitate the gummypolymer; oven-drying (70° C./nitrogen) yielded 2.37 g (24,600 TO/hr;11.8 kg PE/g Ni) clear, rubbery polyethylene. ¹H NMR (CDCl₂CDCl₂; 120°C.): 173 CH₃/1000 CH₂. GPC (TCB; 135° C.; PE standard): Mn=46,000;Mw=103,000; Mz=164,000; Mw/Mn=2.23; Mp=92,100. ¹³C NMR: total Me(179.0); Me (125.1); Et (18.0); Pr (5.4); Bu (9.4); Am (3.3); Hex+ andEOC (17.4).

Ethylene tank pressure drop vs polymerization time (1-L tank) Time, ETank, E Tank min MPa MPa 0.00 3.67 4.74 1.00 3.63 4.67 4.00 3.61 4.6410.0 3.60 4.62 15.00 3.58 4.60 30.00 3.56 4.56 60.00 3.53 4.51

What is claimed is:
 1. A process for the polymerization of one or moreolefins of the formula H₂C═CHR¹ and optionally one or more olefins ofthe formula H₂C═CHR², comprising, contacting said olefins with a complexcontaining a transition metal selected from the group consisting ofpalladium, nickel, titanium, zirconium, scandium, vanadium, chromium,iron, cobalt, and a rare earth metal and a ligand of the formula

which is an active polymerization catalyst, wherein: each R¹ isindependently hydrogen or alkyl; each R² is independently substitutedalkyl or —CO₂R⁵⁰; A and E are each independently oxygen, sulfur,phosphorous or nitrogen; R³ and R⁸ are each independently hydrocarbyl orsubstituted hydrocarbyl provided that the carbon atom bound to thenitrogen atom is bound to at least two other carbon atoms; R⁴, R⁵, R⁶and R⁷ are each independently hydrocarbyl or substituted hydrocarbyl;Ar¹ and Ar² are each independently aryl or substituted aryl; R⁹ and R¹⁰are each independently hydrocarbyl or substituted hydrocarbyl; R⁵⁰ ishydrocarbyl or substituted hydrocarbyl; and provided that: when saidligand is (II) or (III) said transition metal is nickel; when H₂C═CHR²is present a palladium complex is present; the members of any one ormore of the pairs R⁴ and R⁵, R⁶ and R⁷, R⁴ and R⁶, and R⁵ and R⁷ takentogether may form a ring; when said transition metal is palladium, A andE are each independently oxygen, phosphorous or nitrogen; when A isoxygen or sulfur, R⁵ is not present; and when E is oxygen or sulfur, R⁷is not present.
 2. A process for the polymerization of one or moreolefins of the formula H₂C═CHR¹ and optionally one or more olefins ofthe formula H₂C═CHR², comprising, contacting said olefins, a firstcompound of the formula

 [Ar¹HNC(O)OR⁹]MX_(n),  (V) or [Ar¹HNC(O)NHR¹⁰]MX_(n),  (VI) and: (a) asecond compound W, which is a neutral Lewis acid capable of abstractingX⁻ from M to form WX⁻, and which is also capable of transferring analkyl group or a hydride to M, provided that WX⁻ is a weaklycoordinating anion; or (b) a combination of a third compound which iscapable of transferring an alkyl or hydride group to M and a fourthcompound which is a neutral Lewis acid which is capable of abstractingX⁻, a hydride or an alkyl group from M to form a weakly coordinatinganion; or (c) when at least one of X is a hydride or alkyl group, afifth compound which is a cationic Lewis or Bronsted acid whosecounterion is a weakly coordinating anion; wherein: M is Ni, Pd, Ti, Zr,Sc, V, Cr, Fe, Co or a rare earth metal; each X is independently amonoanion; n is equal to the oxidation number of M; each R¹ isindependently hydrogen or alkyl; each R² is independently substitutedalkyl or —CO₂R⁵⁰; A and E are each independently oxygen, sulfur,phosphorous, or nitrogen; R³ and R⁸ are each independently hydrocarbylor substituted hydrocarbyl provided that the carbon atom bound to thenitrogen atom is bound to at least two other carbon atoms; R⁴, R⁵, R⁶and R⁷ are each independently hydrocarbyl or substituted hydrocarbyl;Ar¹ and Ar² are each independently aryl or substituted aryl; R⁹ and R¹⁰are each independently hydrocarbyl or substituted hydrocarbyl; R⁵⁰ ishydrocarbyl or substituted hydrocarbyl; and provided that when saidfirst compound is (II) or (III), M is Ni; the members of any one or moreof the pairs R⁴ and R⁵, R⁶ and R⁷, R⁴ and R⁶, and R⁵ and R⁷ takentogether may form a ring; when H₂C═CHR² is present a palladium complexis present; when M is Pd, A and E are each independently oxygen,phosphorous or nitrogen; when A is oxygen or sulfur, R⁵ is not present;and when E is oxygen or sulfur, R⁷ is not present.
 3. The process asrecited in claim 1 wherein A and E are each independently oxygen,phosphorous or nitrogen.
 4. The process as recited in claim 3 wherein Ais phosphorous or nitrogen.
 5. The process as recited in claim 4 whereinR⁴ and R⁵ taken together form a ring.
 6. The process as recited in claim3 wherein A and E taken together are part of a ring.
 7. The process asrecited in claim 1 wherein said transition metal is Ni, Ti, Zr, Sc, V,Cr or a rare earth metal.
 8. The process as recited in claim 3 whereinsaid transition metal is Ni, Ti, Zr, Sc, V, Cr or a rare earth metal. 9.The process as recited in claim 7 wherein said ligand is (I).
 10. Theprocess as recited in claim 1 wherein said complex is supported on asolid support.
 11. The process as recited in claim 10 wherein said solidsupport is an acidic clay.
 12. The process as recited in claim 1 whereina second active polymerization catalyst is also present.
 13. The processas recited in claim 12 wherein said second active polymerizationcatalyst is a Ziegler-Natta or metallocene catalyst.
 14. The process asrecited in claim 1 wherein a polyolefin is produced and hydrogen is usedto lower the molecular weight of said polyolefin.
 15. The process asrecited in claim 13 wherein a polyolefin is produced and hydrogen isused to lower the molecular weight of said polyolefin.
 16. The processas recited in claim 2 wherein A and E are each independently oxygen,phosphorous or nitrogen.
 17. The process as recited in claim 16 whereinA is phosphorous or nitrogen.
 18. The process as recited in claim 17wherein R⁴ and R⁵ taken together form a ring.
 19. The process as recitedin claim 10 wherein A and E taken together are part of a ring.
 20. Theprocess as recited in claim 2 wherein M is Ni, Ti, Zr, Sc, V, Cr or arare earth metal.
 21. The process as recited in claim 16 wherein saidtransition metal is Ni, Ti, Zr, Sc, V, Cr or a rare earth metal.
 22. Theprocess as recited in claim 20 wherein said first compound is (IV). 23.The process as recited in claim 2 wherein said first compound issupported on a solid support.
 24. The process as recited in claim 23wherein said solid support can take the place of the Lewis or Bronstedacid.
 25. The process as recited in claim 2 wherein a second activepolymerization catalyst is also present.
 26. The process as recited inclaim 25 wherein said second active polymerization catalyst is aZiegler-Natta or metallocene catalyst.
 27. The process as recited inclaim 2 wherein a polyolefin is produced and hydrogen is used to lowerthe molecular weight of said polyolefin.
 28. The process as recited inclaim 16 wherein a polyolefin is produced and hydrogen is used to lowerthe molecular weight of said polyolefin.
 29. The process as recited inclaim 2 wherein W is an alkylaluminum compound.